29,179 results match your criteria Inorganic chemistry[Journal]


Unique Topology Analysis by ToposPro for a Metal-Organic Framework with Multiple Coordination Centers.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Institute of Applied Technology , Dezhou University , Dezhou , Shandong 253023 , P. R. China.

The reactions of 2-(4-pyridyl) thiazole-4-carboxylic acid (Hptca) and CuCl·6HO have led to a novel 3D mixed-valence, four-copper-center, metal-organic framework (MOF) [CuCl(ptca)·17HO] (1). The topology analysis using ToposPro software package for 1 resulted in three chain-based topology types of sra (4, 6, 8), pcu (4, 6), and dia (6) via choosing corresponding connection atoms as central atoms. The study indicates that connection atoms associated directly with multiple coordination centers are applicable to act as central atoms. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03104DOI Listing
February 2019

Porous High-Valence Metal-Organic Framework Featuring Open Coordination Sites for Effective Water Adsorption.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

School of Chemistry and Chemical Engineering , Southeast University , Nanjing 211189 , People's Republic of China.

The design and preparation of a porous high-valence metal-organic framework (MOF) featuring open coordination sites are of utmost importance for the development of adsorbent materials. Here in this work, the three-dimensional (3D) high-valence MOF [Er(dcbp)(DMF)(HO)]·2HO (HV-MOF-1; Hdcbp = 4,4'-dicarboxy-2,2'-bipyridine, DMF = N,N-dimethylformamide), which possesses permanent porosity and two open coordination sites, has been prepared and characterized. In the 3D framework, the dcbp molecules display two different bridging styles, resulting in ordered diamondlike pores with bared carboxyl oxygen and pyridine nitrogen atoms on dcbp exposed directly to the pores, generating hydrophilic characteristics and high water affinity. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03042DOI Listing
February 2019

Valence Variations by B-Site Doping in A-Site Columnar-Ordered Quadruple Perovskites SmMnMn(MnTi )O with 1 ≤ x ≤ 3.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Research Center for Functional Materials , National Institute for Materials Science (NIMS) , Namiki 1-1 , Tsukuba , Ibaraki 305-0044 , Japan.

SmMnMn(MnTi )O with 1 ≤ x ≤ 3 were prepared by a high-pressure, high-temperature method at 6 GPa and about 1570-1670 K. They belong to a family of A-site columnar-ordered quadruple perovskites AA'A″BO, where A' is a site with a square-planar coordination and A″ is a site with a tetrahedral coordination. Their crystal structures were investigated using synchrotron X-ray and neutron powder diffraction. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00049DOI Listing
February 2019

Simultaneous Formation of cis- and trans-CHOCu(OH) Intermediates in Methane Activation by Cu in Solid Ar.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Department of Chemistry and State Key Laboratory of Advanced Textiles Materials and Manufacture Technology, Ministry of Education , Zhejiang Sci-Tech University , Hangzhou 310018 , China.

Understanding the mechanisms of methane activation is an important and active research area of the contemporary catalyzed conversion of hydrocarbons to shippable, valuable feedstock and has invoked close collaborations between experimentalists and theorists. This article describes the trapping of reaction intermediates in a copper-catalyzed direct methane-to-methanol conversion. Specifically, two hydroxy(methoxy)copper(I) [CHOCu(OH)] isomeric intermediates were distinguished and characterized by matrix isolation infrared spectroscopy and O, CD, and CH isotopic substitution experiments combined with quantum chemical calculations. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03322DOI Listing
February 2019

In Situ Formation of Homogeneous Tellurium Nanodots in Paclitaxel-Loaded MgAl Layered Double Hydroxide Gated Mesoporous Silica Nanoparticles for Synergistic Chemo/PDT/PTT Trimode Combinatorial Therapy.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Shaanxi Key Laboratory of Natural Products & Chemical Biology, College of Chemistry & Pharmacy , Northwest A&F University , Yangling , Shaanxi 712100 , People's Republic of China.

A folic acid (FA) functional drug delivery system (MT@L-PTX@FA) based on in situ formation of tellurium nanodots (Te NDs) in paclitaxel (PTX)-loaded MgAl layered double hydroxide (LDHs) gated mesoporous silica nanoparticles (MSNs) has been designed and fabricated for targeted chemo/PDT/PTT trimode combinatorial therapy. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), N adsorption-desorption, Fourier transform infrared (FT-IR) spectra, and UV-vis spectra were used to demonstrate the successful fabrication of MT@L-PTX@FA. In particular, the in situ generated Te NDs showed a homogeneous ultrasmall size. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b02821DOI Listing
February 2019

Balancing between Heterogeneity and Reactivity in Porphyrin Chromium-Cobaltate Catalyzed Ring Expansion Carbonylation of Epoxide into β-Lactone.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Department of Applied Chemistry , Kookmin University , 861-1, Jeongneung-dong, Seongbuk-gu, Seoul 136-702 , Republic of Korea.

The synthesis of a unique heterogeneous catalyst that combines the functionality of a homogeneous catalyst and the advantages of a heterogeneous catalytic process is a continuing goal in various industrially applicable reactions. Here, we report heterogenization of homogeneous catalyst for lactone production from epoxide carbonylation through a facile polymerization using Friedel-Crafts reaction. A correlation between reactivity and degree of heterogeneity has been deduced by synthesizing different sized polymeric catalysts. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03361DOI Listing
February 2019

Control of Excited-State Supramolecular Assembly Leading to Halide Photorelease.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Department of Chemistry , University of North Carolina at Chapel Hill , Murray Hall 2202B , Chapel Hill , North Carolina 27599-3290 , United States.

Ground- and excited-state control of halide supramolecular assembly was achieved through the preparation of a series of ester- and amide-functionalized ruthenium polypyridyl complexes in CHCl. Hydrogen-bonding amide and alcohol groups on the receptor ligand were found to direct interactions with halide, while halide association with the ethyl ester groups was not observed. The various functional groups on the receptor ligands tuned the ground-state equilibrium constants over 2 orders of magnitude (1 × 10 to 1 × 10 M), and the fractional contribution of each hydrogen-bond donor to the total equilibrium constant was determined. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03383DOI Listing
February 2019

Polyanionic Ligand Platforms for Methyl- and Dimethylaluminum Arrays.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Department of Chemistry , University of Liverpool , Crown Street , Liverpool L69 7ZD , U.K.

Trimethylaluminum finds widespread applications in chemical and materials synthesis, most prominently in its partially hydrolyzed form of methylalumoxane (MAO), which is used as a cocatalyst in the polymerization of olefins. This work investigates the sequential reactions of trimethylaluminum with hexaprotic phosphazenes (RNH)PN (=XH) equipped with substituents R of varied steric bulk including tert-butyl (1H), cyclohexyl (2H), isopropyl (3H), isobutyl (4H), ethyl (5H), propyl (6H), methyl (7H), and benzyl (8H). Similar to MAO, the resulting complexes of polyanionic phosphazenates [XH ] accommodate multinuclear arrays of [AlMe] and [AlMe]. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03448DOI Listing
February 2019

Tailored Perovskite Waste Forms for Plutonium Trapping.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Department of Chemistry and Biochemistry , Florida State University , Tallahassee , Florida 32306 , United States.

Perovskite ceramics have been extensively studied as host matrixes for radionuclide entrapment for nuclear waste disposal. As an expansion of these investigations, cerium, neodymium, and plutonium were incorporated into a perovskite phase, ACuFeTiO (A = Nd, Ce, Pu), using sol-gel methods under oxidizing and reducing atmospheres. The targeted materials contained varying levels of Ce and Nd on the A site, yielding potential compositions of NdCe CuFeTiO ( x = 0, 0. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b02832DOI Listing
February 2019

Nickel(II) and Palladium(II) Complexes Bearing an Unsymmetrical Pyrrole-Based PNN Pincer and Their Norbornene Polymerization Behaviors versus the Symmetrical NNN and PNP Pincers.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Department of Chemistry , Indian Institute of Technology Kharagpur , Kharagpur , West Bengal , India 721 302.

Unsymmetrical pincers have been shown to be better than the corresponding symmetrical pincers in several catalysis reactions. A new unsymmetrical PNN propincer, 2-(3,5-dimethylpyrazolylmethyl)-5-(diphenylphosphinomethyl)pyrrole (1), was synthesized from pyrrole through Mannich bases in a good yield. In addition, the new byproduct 2-(3,5-dimethylpyrazolylmethyl)-5-(dimethylaminomethyl)- N-(hydroxymethyl)pyrrole was also isolated. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03562DOI Listing
February 2019

RbAgBiBr: A Lead-Free Visible Light Absorbing Halide Semiconductor with Improved Stability.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Department of Chemistry and Biochemistry , University of Oklahoma , 101 Stephenson Parkway , Norman , Oklahoma 73019 , United States.

Replacement of the toxic heavy element lead in metal halide perovskites has been attracting a great interest because the high toxicity and poor air stability are two of the major barriers for their widespread utilization. Recently, mixed-cation double perovskite halides, also known as elpasolites, were proposed as an alternative lead-free candidate for the design of nontoxic perovskite solar cells. Herein, we report a new nontoxic and air stable lead-free all-inorganic semiconductor RbAgBiBr prepared using the mixed-cation approach; however, RbAgBiBr adopts a new structure type (Pearson's code oP32) featuring BiBr octahedra and AgBr square pyramids that share common edges and corners to form a unique 2D layered non-perovskite structure. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03623DOI Listing
February 2019

Rhombohedral Potassium-Zinc Hexacyanoferrate as a Cathode Material for Nonaqueous Potassium-Ion Batteries.

Inorg Chem 2019 Feb 15. Epub 2019 Feb 15.

Department of Energy Science and Engineering , Daegu Gyeongbuk Institute of Science and Technology , Daegu 42988 , Republic of Korea.

Rhombohedral potassium-zinc hexacyanoferrate KZn[Fe(CN)](HO) (KZnHCF) synthesized using a precipitation method is demonstrated as a high-voltage cathode material for potassium-ion batteries (PIBs), exhibiting an initial discharge capacity of 55.6 mAh g with a discharge voltage of 3.9 V versus K/K and a capacity retention of ∼95% after 100 cycles in a nonaqueous electrolyte. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03081DOI Listing
February 2019

Predictive Strength of Photophysical Measurements for in Vitro Photobiological Activity in a Series of Ru(II) Polypyridyl Complexes Derived from π-Extended Ligands.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Leibniz Institute of Photonic Technology (IPHT) Jena , Department Functional Interfaces , Albert-Einstein-Straße 9 , 07745 Jena , Germany.

This study investigates the correlation between photocytotoxicity and the prolonged excited-state lifetimes exhibited by certain Ru(II) polypyridyl photosensitizers comprised of π-expansive ligands. The eight metal complexes selected for this study differ markedly in their triplet state configurations and lifetimes. Human melanoma SKMEL28 and human leukemia HL60 cells were used as in vitro models to test photocytotoxicity induced by the compounds when activated by either broadband visible or monochromatic red light. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03223DOI Listing
February 2019

Synthesis, Spectroscopy, and Redox Studies of Ferrocene-Functionalized Coinage Metal Alkyne Complexes.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Institute of Inorganic Chemistry , Karlsruhe Institute of Technology , Engesserstraße 15 , D-76131 Karlsruhe , Germany.

Ethynylferrocene (FcC≡CH) was utilized as a redox-active metalloligand for the synthesis of polynuclear coinage metal complexes. The reaction of [FcC≡CLi] with tri- tert-butylphosphine metal chlorides [BuP-MCl] (M = Au, Ag, Cu) yielded different heteronuclear ferrocene-funtionalized alkyne complexes featuring metallophilic interactions. Furthermore, the redox properties of the ferrocenyl-functionalized tetracopper complex were investigated by cyclic voltammetry and UV-vis-near-IR spectroelectrochemistry. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b02873DOI Listing
February 2019

Electronic Structures of an [Fe(NNR)] Redox Series: Ligand Noninnocence and Implications for Catalytic Nitrogen Fixation.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Division of Chemistry and Chemical Engineering , California Institute of Technology , Pasadena , California 91125 , United States.

The intermediacy of metal-NNH complexes has been implicated in the catalytic cycles of several examples of transition-metal-mediated nitrogen (N) fixation. In this context, we have shown that triphosphine-supported Fe(N) complexes can be reduced and protonated at the distal N atom to yield Fe(NNH) complexes over an array of charge and oxidation states. Upon exposure to further H/e equivalents, these species either continue down a distal-type Chatt pathway to yield a terminal iron(IV) nitride or instead follow a distal-to-alternating pathway resulting in N-H bond formation at the proximal N atom. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00133DOI Listing
February 2019

Thiol-Functionalized Pores via Post-Synthesis Modification in a Metal-Organic Framework with Selective Removal of Hg(II) in Water.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Materials Science , Northwest University , Xi'an 710127 , P. R. China.

Owing to the rapid increase of Hg(II) ions in water resources, the design and development of new adsorbents for Hg(II) removal are becoming a significant challenge in environmental protection. Herein, a thiol-functionalized metal-organic framework (SH-MiL-68(In)) was successfully prepared through a post-synthesis modification procedure, and the framework intactness and porosity were well maintained after this process. SH-MiL-68(In) exhibited selective adsorption performance for Hg(II) ions in water. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03505DOI Listing
February 2019

Three Types of Distinguishing l-Alanine-Decorated and Rare-Earth-Incorporated Arsenotungstate Hybrids Prepared in a Facile One-Step Assembly Strategy.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering , Henan University , Kaifeng , Henan 475004 , People's Republic of China.

Three kinds of distinguishing ala-decorated RE-incorporated (ala = l-alanine, RE = rare-earth) polytungstoarsenate hybrids containing {AsWO} building blocks [HN(CH)]NaH[EuW(HO)(ala)O(AsWO)]·35HO (1), [HN(CH)]NaH[REW(HO)(ala)O(OH)(AsWO)]·36HO [RE = Gd (2), Tb (3)], and [HN(CH)]Na[REW(HO)(ala)O(OH)(AsWO)]·40HO [RE = Dy (4), Ho (5), Er (6), Yb (7), Lu (8)] were made in a facile one-step assembly strategy. The polyoxoanion skeletons of 1-8 are very similar, and all can be described as two [AsWO] moieties encapsulating an ala-decorated W-O-RE heterometallic cluster ([EuW(HO)(ala)O] for 1, [REW(HO)(ala)O(OH)] for 2-3, and [REW(HO)(ala)O(OH)] for 4-8, resulting in a four-leaf--clover-shaped tetrameric structure; however, the major discrepancy in the ala-decorated W-O-RE heterometallic clusters lies in the number of ala molecules equaling to three, four, and two, which may result from the various coordination geometries of RE ions and the different construction modes of W-O-RE heterometallic clusters. It should be emphasized that the carboxyl groups of ala ligands only coordinate to the W centers in 4-8, while they not only bridge the W centers together but also combine RE ions together in 1-3. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00004DOI Listing
February 2019

Triangular Rare-Earth Lattice Materials RbBa R(BO) ( R = Y, Gd-Yb) and Comparison to the KBa R(BO) Analogs.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Department of Chemistry , Princeton University , Princeton , New Jersey 08544 , United States.

A previously unreported family of electrically insulating rare-earth borates, RbBa R(BO) ( R = Y, Gd-Yb), was designed and then successfully obtained by traditional solid-state reaction. They crystallize in a monoclinic crystal system space group P2 /m (No. 11). Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03372DOI Listing
February 2019

BaCrNH: A New Nitride-Hydride with Trigonal Planar Cr.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

National High Magnetic Field Laboratory , Tallahassee , Florida 32310 , United States.

The nitride-hydride BaCrNH was obtained in single crystalline form using flux growth techniques based on alkaline earth metals. BaCrNH crystallizes in the hexagonal space group P6/ m (Nr 176), with the lattice parameters a = 8.0270(2) Å, c = 5. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03367DOI Listing
February 2019

Insights into Single-Molecule-Magnet Behavior from the Experimental Electron Density of Linear Two-Coordinate Iron Complexes.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Department of Chemistry & Centre for Materials Crystallography , Aarhus University , DK-8000 Aarhus C , Denmark.

A breakthrough in the study of single-molecule magnets occurred with the discovery of zero-field slow magnetic relaxation and hysteresis for the linear iron(I) complex [Fe(C(SiMe))] (1), which has one of the largest spin-reversal barriers among mononuclear transition-metal single-molecule magnets. Theoretical studies have suggested that the magnetic anisotropy in 1 is made possible by pronounced stabilization of the iron d orbital due to 3d -4s mixing, an effect which is predicted to be less pronounced in the neutral iron(II) complex Fe(C(SiMe)) (2). However, experimental support for this interpretation has remained lacking. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03301DOI Listing
February 2019

Postsynthetic Metal Exchange in a Metal-Organic Framework Assembled from Co(III) Diphosphine Pincer Complexes.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Department of Chemistry and Biochemistry , The Ohio State University , Columbus , Ohio 43210 , United States.

A Zr metal-organic framework (MOF) 1-CoCl has been synthesized by solvothermal reaction of ZrCl with a carboxylic acid-functionalized Co-PNP pincer complex H(L-CoCl) ([L-CoCl] = [(2,6-(NHPAr)CH)CoCl], Ar = p-CHCO). The structure of 1-CoCl has been determined by X-ray powder diffraction and exhibits a csq topology that differs from previously reported ftw-net Zr MOFs assembled from related Pd- and Pt-PNP pincer complexes. The Co-PNP pincer species readily demetallate upon reduction of Co to Co, allowing for transmetalation with late second and third row transition metals in both the homogeneous complex and 1-CoCl. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03318DOI Listing
February 2019

Capturing a Square Planar Gold(III) Complex Inside a Platinum Nanocage: A Combined Experimental and Theoretical Study.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Sorbonne Université-Faculté des Sciences et Ingénerie Campus Pierre et Marie Curie, CNRS, IPCM (UMR 8232) , 4 place Jussieu , 75252 Paris cedex 05 , France.

A novel synthetic procedure was set up to gain access to platinum coordination cages PtL, which are less investigated compared to their palladium counterparts. This PtL nanocage exhibits an adequate cavity for guest encapsulation. Indeed, the Au(III) metal complex [Au(bdt)] (bdt = benzene-1,2-dithiolate) was successfully captured inside the cavity, in contrast to the analogous palladium cage which failed to host the gold complex. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03272DOI Listing
February 2019

Polymerization Isomerism in [{MFe(CO)} ] (M = Cu, Ag, Au; n = 3, 4) Molecular Clusters Supported by Metallophilic Interactions.

Inorg Chem 2019 Feb 14. Epub 2019 Feb 14.

Dipartimento di Chimica Industriale "Toso Montanari" , Università di Bologna , Viale Risorgimento 4 , 40136 Bologna , Italy.

Triangular clusters [{MFe(CO)}] (M = Cu, 4; Ag, 5; Au, 6) were selectively obtained by heating Fe(CO)(MIMes) (M = Cu, 1; Ag, 2; Au, 3; IMes = CNH(CHMe)). 1-3 were synthesized by reacting Na[Fe(CO)]·2thf with 2 equiv of M(IMes)Cl. As previously described, the direct reactions of Na[Fe(CO)]·2thf with one equivalent of M(I) salts resulted in the triangular cluster [{CuFe(CO)}] for Cu, whereas the square clusters [{MFe(CO)}] were formed for Ag and Au. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03334DOI Listing
February 2019

Zeolitic Open-Framework Borates with Noncentrosymmetric Structures and Nonlinear Optical Properties.

Inorg Chem 2019 Feb 13. Epub 2019 Feb 13.

College of Chemistry and Chemical Engineering , Qingdao University , Shandong 266071 , P.R. China.

Three zeolitic pentaborates (Hen)[BO(OH)] (1, en = ethylenediamine), (Hen)[Al(BO)] (2), (Hen)[NH(CH)][Al(BO)] (3) were solvothermally obtained by employing ethanediamine molecules as structure-directing agents (SDAs). The nonmetal borate of 1 features a noncentrosymmetric two-dimensional layered structure. Through introducing Al atoms as the linkers and regulating the reaction conditions of 1, two three-dimensional zeolitic open-framework aluminoborates, noncentrosymmetric (NCS) of 2 and centrosymmetric (CS) of 3, were achieved. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00101DOI Listing
February 2019

Two-Dimensional Excitonic Metal-Organic Framework: Design, Synthesis, Regulation, and Properties.

Inorg Chem 2019 Feb 13. Epub 2019 Feb 13.

Key Laboratory of Medicinal Chemistry for Natural Resource Education Ministry , Yunnan University , Kunming 650091 , People's Republic of China.

A family of two-dimensional (2D) Zn-based metal-organic frameworks (MOFs) with exitonic emission have been successfully synthesized under hydrothermal conditions. When isophthalic acid ligands with different substitutions are introduced, the crystal structures and fluorescence properties are significantly changed. Hirshfeld surface calculation is used to study the nuances of diverse substitutions during the construction of all of the crystals. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03210DOI Listing
February 2019

Stabilization of a Cyclometalated Ruthenium Sensitizer on Nanocrystalline TiO by an Electrodeposited Covalent Layer.

Inorg Chem 2019 Feb 13. Epub 2019 Feb 13.

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences , Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190 , China.

A cyclometalated ruthenium sensitizer 3 containing a triphenylamine unit was synthesized and immobilized on a nanocrystalline TiO surface. By using oxidative electrochemical deposition, a covalent layer of a related cyclometalated ruthenium complex 2 was coupled to the top of dye 3. Electrochemical studies suggested that complex 2 was immobilized on the TiO/3 film surface by a tetraphenylbenzidine linker to form a dimer-like structure. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00092DOI Listing
February 2019

Multifunctional Copper(I) Coordination Polymers with Aromatic Mono- and Ditopic Thioamides.

Inorg Chem 2019 Feb 12. Epub 2019 Feb 12.

Instituto Madrileño de Estudios Avanzados en Nanociencia , Cantoblanco, Madrid 28049 , Spain.

Direct reactions under ambient conditions between CuX (X = Br, I) and thiobenzamide (TBA) were carried out at different ratios, giving rise to the formation of a series of one-dimensional (1D) coordination polymers, (CPs) [CuI(TBA)] (1), [CuI(TBA)] (4), and [CuBr(TBA)] (5), as well as two molecular complexes, [CuI(TBA)] (2) and [CuI(TBA)]·2MeCN (3). Recrystallization of 1 and 5 yielded a series of isostructural 1D CP solvated species, [CuI(TBA)·S] ] (1·S; S = tetrahydrofuran, acetone, methanol) and [CuBr(TBA)·S] (5·S; S = tetrahydrofuran, acetone), respectively. Similar reactions between CuI and 1,4-dithiobenzamide (DTBA) allowed the isolation of a series of two-dimensional (2D) CPs [CuI(DTBA)·S] (6·S; S = N, N-dimethylformamide, acetonitrile, methanol). Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03364DOI Listing
February 2019
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Hierarchical NiP@NiFeAlO Nanosheet Arrays as Bifunctional Catalysts for Superior Overall Water Splitting.

Inorg Chem 2019 Feb 12. Epub 2019 Feb 12.

State Key Laboratory of Nuclear Resources and Environment, School of Chemistry, Biology and Materials Science , East China University of Technology , Nanchang 330013 , P. R. China.

Bifunctional electrocatalysts based on transition-metal phosphides are appealing for overall water splitting owing to their excellent electrical conductivity, low cost, and high stability. However, these specials are often restricted by some serious drawbacks such as its relatively poor activity for oxygen evolution reaction (OER) and its manufacture, which usually requires one to add additional large numbers of P sources and, consequently, inevitably leads to the release of flammable and detrimental PH. Herein, we show an effective avenue to overcome these issues. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03327DOI Listing
February 2019
1 Read

Molecular Hydroxo-Bridged Dimers of Uranium(VI), Neptunium(VI), and Plutonium(VI): [MeN][(AnO)(OH)(NO)].

Inorg Chem 2019 Feb 12. Epub 2019 Feb 12.

Chemical Sciences and Engineering Division , Argonne National Laboratory , Argonne , Illinois 60439 , United States.

The synthesis of a series of molecular actinyl(VI), namely, uranium(VI), neptunium(VI), and plutonium(VI), hydroxo-bridged dimers is reported. These complexes were isolated from an aqueous nitrate solution by titration with tetramethylammonium hydroxide. The solid-state structures were determined using single-crystal X-ray diffraction, revealing molecular complexes with the formula [MeN][(AnO)(μ-OH)(NO)], where An = U, Np, and Pu. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03304DOI Listing
February 2019

Hydrogen Evolution in [NiFe] Hydrogenases: A Case of Heterolytic Approach between Proton and Hydride.

Inorg Chem 2019 Feb 12. Epub 2019 Feb 12.

Science & Technology Innovation Institute , Dongguan University of Technology , Dongguan 523808 , China.

The mechanism for Hydrogen Evolution Reaction (HER) in [NiFe] hydrogenase enzymes distinguishes them from inorganic catalysts. The first H/e pair injected to the active site of the hydrogenases transforms into hydride, while the second H/e pair injection leads to the formation of the H/H pair both binding to the active site. The two opposite charged hydrogens heterolytically approach each other in order to form dihydrogen (H), which is enhanced by the Coulomb force. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b02812DOI Listing
February 2019
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Xantphos-Capped Pd(II) and Pt(II) Macrocycles of Aryldithiolates: Structural Variation and Catalysis in C-C Coupling Reaction.

Inorg Chem 2019 Feb 11. Epub 2019 Feb 11.

Department of Chemistry , Texas A&M University , P.O. Box 30012, College Station , Texas 77842-3012 , United States.

The self-assembly of Xantphos-capped M(OTf) (M = cis-[M'(Xantphos)]; M' = Pd, Pt) with bridging ligands 1,4-benezenedithiol or 4,4'-biphenyldithiol has been investigated. The reactions have yielded complexes [M{S(CH) SH}](OTf) (I) and [M{S(CH) S}](OTf) (II) ( n = 1 or 2). The equilibrium between I and II has been established in platinum complexes for n = 2, whereas the analogous Pd complex exclusively exist as II. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b02726DOI Listing
February 2019
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MnO Nanoparticles Sandwiched within 3D Graphene-Based Hierarchical Architecture for Efficient Lithium Storage.

Inorg Chem 2019 Feb 11. Epub 2019 Feb 11.

School of Metallurgy and Environment , Central South University , Changsha 410083 , China.

Manganese monoxide (MnO) has drawn considerable attention as anode candidate for lithium-ion batteries (LIBs) due to its high theoretical capacity of 755.6 mAh g (over twice as much as graphite) and relatively low voltage hysteresis. However, some challenging issues such as poor cyclic performance and inferior rate capability caused by the limited reaction kinetics, severe particle agglomeration of MnO, and large volume expansions during cycling still hampered its commercial implementation. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03390DOI Listing
February 2019

Theoretical Studies on Hexanuclear [M(μ-O/OH)] (M = Fe(III), Mn(III), and Ni(II)) Clusters: Magnetic Exchange, Magnetic Anisotropy, and Magneto-Structural Correlations.

Inorg Chem 2019 Feb 11. Epub 2019 Feb 11.

Department of Chemistry , Indian Institute of Technology Bombay , Powai, Mumbai , Maharashtra , India - 400076.

Controlling spin Hamiltonian parameters such as magnetic exchange and magnetic anisotropy of polynuclear clusters is of great interest in the area of single molecule magnets (SMMs). Among large polynuclear clusters, hexanuclear clusters offer the best compromise in terms of size as they are often rigid, solution stable, and chemically amenable. The {MO} core is one of the common architectures known for many hexanuclear clusters and generally reported to possess a diamagnetic S = 0 spin ground state, barring a few exceptions. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03257DOI Listing
February 2019

Silylated Ge Clusters as New Ligands for Cyclic (Alkyl)amino and Mesoionic Carbene Copper Complexes.

Inorg Chem 2019 Feb 11. Epub 2019 Feb 11.

Department of Chemistry , Technische Universität München (TUM) , Lichtenbergstraße 4 , 85748 Garching , Germany.

The coordination of Ge Zintl clusters at (carbene)Cu moieties is explored, and the complexes [(CAAC)Cu][η-Ge{Si(TMS)}] (1), (CAAC)Cu[η-Ge{Si(TMS)}] (2), and (MIC)Cu[η-Ge{Si(TMS)}] (3) are compared with their known N-heterocyclic carbene (NHC) derivatives (A and B), where CAAC = cyclic (alkyl)amino carbene, MIC = mesoionic carbene, and TMS = trimethylsilane. In analogy to the NHC derivatives, the synthesis of 1-3 proceeds by single-step reactions of (CAAC)CuCl or (MIC)CuCl with the [GeR] and [GeR] [R = Si(TMS)] cluster ligands, respectively, and yields complexes of (carbene)Cu (carbene = CAAC, MIC) moieties exhibiting η-coordination modes of the Ge deltahedron to the Cu atom. In 1, [GeR] acts as a η-bridging unit for two (CAAC)Cu moieties, and 2 and 3 feature single (carbene)Cu (CAAC and MIC) fragments η-connected to [GeR] units. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03338DOI Listing
February 2019

Uranyl Compounds Involving a Weakly Bonded Pseudorotaxane Linker: Combined Effect of pH and Competing Ligands on Uranyl Coordination and Speciation.

Inorg Chem 2019 Feb 11. Epub 2019 Feb 11.

Laboratory of Nuclear Energy Chemistry , Institute of High Energy Physics, Chinese Academy of Sciences , Beijing 100049 , P. R. China.

Pseudorotaxane-type ligands with tunable structural dynamics offer an opportunity in the exploration of new actinide hybrid materials. In this work, we utilized a weakly bonded pseudorotaxane ligand involving CB[6] and 1, 1'-(heptane-1, 7-diyl)bis(4-(ethoxycarbonyl)pyridin-1-ium) bromides ([C7BPCEt]Br@CB[6]) to assemble with uranyl ion, and we systematically investigated the effect of different factors including pH and competing ligands on the hydrothermal synthesis of URCPs. Nine uranyl-rotaxane coordination polymers (URCPs) with diversity in coordination mode and topological structure were successfully prepared (two previously reported complexes, URCP1 and URCP2 are also included). Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03353DOI Listing
February 2019

Role of Phosphine Sterics in Strained Aminophosphine Chelate Formation.

Inorg Chem 2019 Feb 11. Epub 2019 Feb 11.

Department of Chemistry , The University of British Columbia , Vancouver , British Columbia V6T 1Z1 , Canada.

The preparation of four-membered aminophosphine (PN) chelates from common metal precursors has largely evaded realization because of the ring strain associated with these species. We report a straightforward approach to the synthesis of such PN metallacycles using simple α-PN ligands analogous to the popular class of small-bite-angle diphosphinomethane ligands. It is demonstrated that bulky phosphine substituents are important to the formation of these chelates. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03514DOI Listing
February 2019

3-Hydroxy-2-Pyrrolidinone as a Potential Bidentate Ligand for in Vivo Chelation of Uranyl with Low Cytotoxicity and Moderate Decorporation Efficacy: A Solution Thermodynamics, Structural Chemistry, and in Vivo Uranyl Removal Survey.

Inorg Chem 2019 Feb 8. Epub 2019 Feb 8.

State Key Laboratory of Radiation Medicine and Protection, School for Radiological and Interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions , Soochow University , Suzhou 215123 , P. R. China.

Uranium poses a threat for severe renal and bone damage in vivo. With the rapid development of nuclear industry, it is more urgent than ever to search for potential in vivo uranium chelators. In this work, 3-hydroxy-2-pyrrolidinone (HPD) is investigated as a new potential uranium decorporation ligand. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.8b03442
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http://dx.doi.org/10.1021/acs.inorgchem.8b03442DOI Listing
February 2019
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Two 3D Cobalt(II) Metal-Organic Frameworks with Micropores for Selective Dye Adsorption.

Inorg Chem 2019 Feb 8. Epub 2019 Feb 8.

Tianjin Key Laboratory of Structure and Performance for Functional Molecules and Key Laboratory of Inorganic-Organic Hybrid Functional Materials Chemistry, MOE, College of Chemistry , Tianjin Normal University , Tianjin 300387 , P. R. China.

Two porous coordination polymers, {[Co(TBC)]·2DMF} (1) and {[Co(TBC)Cl(CHOH)]·0.5Cl} (2), were synthesized via the solvothermal reaction of cobalt(II) salts and 3,5-bis(1 H-1,2,4-triazol-1-yl)benzenecarboxylic acid. Single-crystal X-ray diffraction analyses exhibited that complex 1 contains rtl three-dimensional (3D) skeleton and one-dimensional channels with large apertures, while complex 2 displays a novel 2-nodal 3,6-linked 3D structure with a Schläfli sign of {4. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03194DOI Listing
February 2019

Influence of the Counterion on the Synthesis of Cyclic Carbonates Catalyzed by Bifunctional Aluminum Complexes.

Inorg Chem 2019 Feb 8. Epub 2019 Feb 8.

Departamento de Química Inorgánica, Orgánica y Bioquímica-Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologías Químicas , Universidad de Castilla-La Mancha , 13071 Ciudad Real , Spain.

New bifunctional aluminum complexes have been prepared with the aim of studying the effect of a counterion on the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO). Neutral ligand 1 was used as a precursor to obtain four novel mesylate, chloride, bromide, and iodide zwitterionic NNO ligands (2-5). The reaction of these ligands with 1 or 2 equiv of AlR (R = Me, Et) allowed the synthesis of mono- and bimetallic bifunctional aluminum complexes [AlR(κ-mbpzappe)]X [X = Cl, R = Me (6), Et (7); X = Br, R = Me (8), Et (9); X = I, R = Me (10), Et (11)] and [{AlR(κ-mbpzappe)}(μ-O){AlR}]X [X = MeSO, R = Me (12), Et (13); X = Cl, R = Me (14), Et (15); X = Br, R = Me (16), Et (17); X = I, R = Me (18), Et (19)] via alkane elimination. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03475DOI Listing
February 2019

Induction of Enzyme-like Peroxidase Activity in an Iron Porphyrin Complex Using Second Sphere Interactions.

Inorg Chem 2019 Feb 8. Epub 2019 Feb 8.

Department of Inorganic Chemistry , Indian Association for the Cultivation of Science , Kolkata , India 700032.

Emulating enzymatic reactivity using small molecules has been a long-time challenging pursuit of the scientific community. Peroxidases, ubiquitous heme enzymes that are involved in hormone synthesis and the immune system, have been a prime target of such efforts due to their tremendous potential in the chemical industry as well as in wastewater treatment. Here it is demonstrated that inclusion of a second sphere guanidine moiety in an iron porphyrin not only makes this small molecule a veritable peroxidase catalyst but also offers an auxiliary binding site for organic substrates, facilitating their rapid oxidation with a green oxidant like HO. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b02707DOI Listing
February 2019

Interaction between Bi Dopants and Intrinsic Defects in LiNbO from Local and Hybrid Density Functional Theory Calculations.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

State Key Lab of Crystal Materials and Institute of Crystal Materials , Shandong University , Jinan 250100 , China.

The interactions between Bi dopants including Bi-substituting Li (Bi) and Bi-substituting Nb (Bi) and the intrinsic antisite defects (Nb) and Li vacancies (V) in LiNbO are investigated using local and hybrid density functional theories. Three charge-compensated defect clusters, Bi + Nb + 8V, Bi + 4V, and Bi + Bi + 4V, are modeled in this work to investigate the effects of the Bi concentration. The most stable cluster configurations, the Bi-doping stability in the clusters, and the electronic state interaction between Bi and intrinsic defects have been studied in detail. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03167DOI Listing
February 2019

Effects of Lewis Acidic Metal Ions (M) on Oxygen-Atom Transfer Reactivity of Heterometallic MnMO Cubane and FeMO(OH) and MnMO(OH) Clusters.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

Department of Chemistry , University of California , Davis , California 95616 , United States.

The modulation of the reactivity of metal oxo species by redox inactive metals has attracted much interest due to the observation of redox inactive metal effects on processes involving electron transfer both in nature (the oxygen-evolving complex of Photosystem II) and in heterogeneous catalysis (mixed-metal oxides). Studies of small-molecule models of these systems have revealed numerous instances of effects of redox inactive metals on electron- and group-transfer reactivity. However, the heterometallic species directly involved in these transformations have rarely been structurally characterized and are often generated in situ. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b02701DOI Listing
February 2019
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Relativistic Effects on a Metal-Metal Bond: Osmium Corrole Dimers.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

Department of Chemistry , UiT - The Arctic University of Norway , N-9037 Tromsø , Norway.

A series of metal-metal bonded osmium corrole dimers, {Os[T pXPC]}, were synthesized in reasonably good yields (35-46%) via the interaction of the corresponding free-base meso-tris( p-X-phenyl)corroles (H[T pXPC], X = CF, H, CH, and OCH), Os(CO), and potassium carbonate in 1,2,4-trichlorobenzene under an inert atmosphere at 180 °C over several hours. The complexes are only the second class of Os corroles reported to date (the first being OsN corroles) and also the second class of metal-metal bonded metallocorrole dimers (the other being Ru corrole dimers). Comparison of the X-ray structures, redox potentials, and optical spectra of analogous Ru and Os corrole dimers, along with scalar-relativistic DFT calculations, has provided an experimentally calibrated account of relativistic effects in these complexes. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03391DOI Listing
February 2019

Multi-Emissive Lanthanide-Based Coordination Polymers for Potential Application as Luminescent Bar-Codes.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

Univ Rennes, INSA Rennes, ENSCR, CNRS UMR6226 "Institut des Sciences Chimiques de Rennes″ , F-35000 Rennes , France.

Isostructural lanthanide-based coordination polymers that are obtained by reactions in water of a lanthanide chloride and the sodium salt of 5-methoxyisophthalate (mip) have the general chemical formula [Ln(mip)(HO)·4HO] with Ln = Nd-Er except Pm plus Y (symbolized by [Ln(mip)]). Some of these homo-lanthanide compounds present very high luminescence brightness. The weak intermetallic energy transfer between lanthanide ions observed in these compounds allows the design of hetero-lanthanide coordination polymers with tunable luminescence properties. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03277DOI Listing
February 2019

Synthesis of closo-1,2-HCBMe and 1,2-HCBMeX (X = I and OTf) Dicarbaboranes and Their Rearrangement Reactions.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

Institute of Inorganic Chemistry of the Czech Academy of Sciences , 250 68 Husinec-Řež , Czech Republic.

Methyl-camouflaged dicarbaboranes closo-1,2- and 1,10-HCBMe have been prepared in high yields either from nido-5,6-HCBH or closo-1,2-HCBH via electrophilic methylation reactions and cluster-rearrangement methods. Prepared were also monosubstituted derivatives of general formulation closo-HCBMe-X (X = I or OTf). The permethylated compounds exhibit extreme air stability in comparison to unprotected counterparts as a consequence of rigid, egg-shaped hydrocarbon structures incorporating inner CB carborane scaffolding. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03550DOI Listing
February 2019
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Exploring the Magnetic Interaction of Asymmetric Structures Based on Chiral V Clusters.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

College of Chemical Engineering, State Key Laboratory of Materials-oriented Chemical Engineering , Nanjing Tech University , Nanjing , 210009 , China.

Polyoxovanadates (III) are important class of polyoxometalates in molecular magnetism field, and particularly the systems which contain vanadium(III) centers. To date, only very few highly reduced vanadium polynuclear complexes were reported, which remains a significant challenge to synthesize novel polyoxovanadates, owing to the characteristics of easily oxidized vanadium(III). Herein, two unprecedented petaloid chiral octanuclear polyoxovanadates, l- and d-[HN(CH)](HN(CH)NH)(HO)(Vμ-OH)(SO)·2HO (L-, D-V), have been successfully obtained by solvothermal method without any chiral auxiliary. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03220DOI Listing
February 2019
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Solid-State Electrochemistry of Copper(I) Coordination Polymers Containing Tetrafluoroborate Anions.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

Toyota Central R&D Laboratories, Inc. , 41-1 Yokomichi , Nagakute , Aichi 480-1192 , Japan.

Host-guest materials based on coordination polymers (CPs) are currently emerging as potential candidates for battery applications. In this context, we describe the preparation of three-dimensional network structures containing BF anions and water molecules in the one-dimensional (1D) channels via hydrothermal reactions between Cu(BF) and 4,4'-bipyridine or 1,2-di-4-pyridylethylene. A systematic characterization of the obtained CPs using single-crystal X-ray diffraction, X-ray absorption fine structure, and an electrochemical test was performed. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b02768DOI Listing
February 2019

Magnetic Ground State Crossover in a Series of Glaserite Systems with Triangular Magnetic Lattices.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

Department of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET) , Clemson University , Clemson , South Carolina 29634-0973 , United States.

The magnetic properties are reported for three members of the glaserite series of compounds, NaBaM(VO), M = Mn, MnCo, and Co. Large single crystals are grown using a high-temperature hydrothermal synthesis method. This structure type exhibits a triangular magnetic lattice in which MO octahedra are interconnected with nonmagnetic (VO) groups. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03418DOI Listing
February 2019

Superhydrophobic/Superoleophilic MOF Composites for Oil-Water Separation.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

College of Chemistry , Liaoning University , Shenyang 110036 , P. R. China.

A universal strategy is developed to construct metal-organic framework (MOF)-based superhydrophobic/superoleophilic materials by the reaction of activated MOFs and octadecylamine. In particular, S-MIL-101(Cr) composite can efficiently separate chloroform, toluene, petroleum ether, and n-hexane from water with excellent oil-water separation performance, with potential application in the environmental field. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03293DOI Listing
February 2019

Lattice Water Controlled Photo- and Thermochromism of N-Protonated Carbomethoxypyridinium Iodoargentate Hybrids.

Inorg Chem 2019 Feb 7. Epub 2019 Feb 7.

Key Laboratory of Magnetic Molecules, Magnetic Information Materials Ministry of Education, School of Chemical and Material Science , Shanxi Normal University , Linfen 041004 , China.

Two iodoargentate hybrids, {[HNOM][AgI]·HO} (1) and {[HINOM][AgI]·HO} (2) (HNOM = N-protonated 3-carbomethoxypyridinium; HINOM = N-protonated 4-carbomethoxypyridinium), have been designed and prepared, which were constructed from typical [AgI] inorganic chains and cationic hydrogen-bonding supramolecular networks (one-dimensional for 1 and three-dimensional for 2) of lattice water and positional isomeric N-protonated carbomethoxypyridinium. Two hybrids exhibit sensitive photochromism based on intermolecular electron transfer (ET) and thermochromism due to reversible hydration and dehydration and the consequent variation of intermolecular charge transfer (CT). Furthermore, loss of lattice water gives rise to improved photochromic dehydrated form 1T and optically inert dehydrated form 2T, suggesting a delicate modulating effect of lattice contraction on the intermolecular CT and ET as well as consequently photoresponsive behaviors. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03450DOI Listing
February 2019
1 Read